CN108083818B - Structure-enhanced photocuring resin-based ceramic composite material and blank degreasing method - Google Patents
Structure-enhanced photocuring resin-based ceramic composite material and blank degreasing method Download PDFInfo
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- CN108083818B CN108083818B CN201711483908.2A CN201711483908A CN108083818B CN 108083818 B CN108083818 B CN 108083818B CN 201711483908 A CN201711483908 A CN 201711483908A CN 108083818 B CN108083818 B CN 108083818B
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/638—Removal thereof
Abstract
The invention discloses a structure-enhanced photocuring resin-based ceramic composite material and a degreasing method of a ceramic blank. By optimally designing the resin system, the transmission depth of the ceramic slurry system can be improved and the forming size error can be reduced while the reaction activity of the system is kept; the bonding force between the ceramic blank layers and the printing platform are increased, and the separation of the ceramic blank from the platform and the cracks on the surface of the ceramic blank are reduced; and meanwhile, the tensile strength of the formed part is improved, so that the material can meet the printing requirements of suspension and fine structures.
Description
Technical Field
The invention relates to the field of ceramic materials, in particular to a photocuring resin-based ceramic composite material with improved tensile property for additive forming and a degreasing method of a ceramic blank prepared from the photocuring resin-based ceramic composite material.
Background
Additive manufacturing (also referred to as "3D printing") is a manufacturing process that generates three-dimensional objects from digital files. During 3D printing, layers of material are successively superimposed until the final object form is formed. Each layer can be regarded as a thin cross-section of the object, and the thickness of each layer determines the printing accuracy, the smaller the layer thickness, the higher the printing accuracy, and the closer the printed entity is to the digital model itself.
The precision and efficiency of additive forming are very closely related to additive materials, and additive materials are a research hotspot in the field of additive manufacturing. The ceramic material has excellent performances for various structures and building applications, such as good heat resistance, elasticity, plasticity, tensile strength, compressive strength, shear strength and the like, the 3D printing ceramic can omit the whole process of the traditional manual molding and modeling, can finish a three-dimensional structure which cannot be realized by the traditional ceramic industry with higher precision, has the advantages of high molding speed, printable complex parts, low cost of personalized products and the like, has the characteristics of stable performance, sterility and the like, can be used for preparing products with small size, complex shape and high precision, such as ceramic pins for optical connectors, electronic ceramic devices, multi-hollow ceramic filter pieces, ceramic teeth and the like, and therefore, the ceramic material for additive molding is an important additive development direction at present. For example, in chinese patent application No. CN201610398978.7, a three-dimensional printing composite material is disclosed, in which it is indicated that a composite material formed by adding ceramic powder to a light-curing resin can be printed out by means of light-curing molding (SLA) or Digital Light Processing (DLP) to form an object having ceramic luster and texture directly on the surface.
The improvement of the composition of ceramic slurry in chinese invention patent application No. CN201510590675 provides a method that can still be used to make highly dense ceramics when the solids content of the slurry is below 40 vol%. Chinese patent application No. CN201710035091 discloses a method for preparing ceramic slurry for photo-curing, wherein it is proposed to disperse 25-85 vol% of ceramic powder into 15-75 vol% of photosensitive resin premix system to obtain ceramic slurry with high solid content and low viscosity, thereby solving the problems of cracks or deformation caused by high shrinkage of the final ceramic product due to low solid content. US2015/0111176a1 discloses a resin composite and a method of use thereof, wherein the material composition is improved in terms of the maximum absorption wavelengths of the two initiators and the absorber.
However, the existing photocurable ceramic composite material for additive molding usually requires 45-65 vol% of ceramic powder material. The high content of inorganic inert powder material enables the viscosity of the ceramic slurry system to be larger, and literature data shows that the viscosity of the ceramic slurry system suitable for DLP 3D printing and forming is less than 3 Pa.S. The inventor finds that when the viscosity of the ceramic slurry system exceeds 1Pa.S, the adhesive force between the printing platform and the release film of the ceramic blank and the trough is too large, and the ceramic blank and the printing platform are frequently separated; the inventor also finds that the components of the ceramic composite material with high inert powder content shrink unevenly after being cured, and the composite material has large stress after being cured, so that the internal cohesive force of the composite material is reduced after being cured, and cracks appear on the surface of a ceramic blank due to the existence of interlayer stress. Meanwhile, the addition of the ceramic powder greatly weakens the binding power between the organic binder and the printing platform, and the reduction of the binding power is also an important reason for frequently causing the separation of the ceramic blank and the printing platform in the printing and forming process, thereby causing printing failure. In addition, in the conventional photocurable ceramic composite material for additive molding, light scattering due to a refractive index difference between the ceramic powder and the resin binder is also a main cause of deviation in precision in the ceramic slurry additive molding process.
Further, the applicant has found that when a large amount of powder is added to the resin system, a significant decrease in the tensile strength of the molded article results, which may cause the partial suspended structure and the fine structure to crack during the printing process and even make the molding difficult.
Disclosure of Invention
Aiming at the problems in the prior art, the resin slurry is optimally designed, and particularly, resin monomers and cross-linking agent components with proper polarity and refractive index, a powder stabilizer, a polymerization anti-interference agent, an interface reinforcing agent, a low-temperature pore-forming agent, a structure reinforcing agent and other components are selected, so that a ceramic slurry system has low viscosity performance (less than 1Pa.S) more suitable for 3D printing, the smaller refractive index difference between the resin slurry and the ceramic powder acts together with the polymerization anti-interference agent, the transmission depth Cd of the ceramic slurry system is greatly improved, and the size error and the interlayer stress caused by light scattering in the forming process are effectively reduced; the active monomer and the ceramic powder material have better affinity, and after the active monomer and the crosslinking component are cured, stronger intermolecular forces such as hydrogen bonds and the like can be formed, so that the bonding force between ceramic blank layers is increased, the bonding force between the ceramic blank and a metal printing platform is correspondingly increased, the stronger bonding force and the smaller release force of the platform, the model and the release film under lower system viscosity act together, the separation phenomenon of the ceramic blank and the platform is effectively reduced, and the surface crack phenomenon of the ceramic blank is well solved; meanwhile, with the help of the structural reinforcing agent and the dosage which are matched with the resin system, the tensile strength of the formed part can be greatly improved, and the normal printing of suspended structures and micro-structure models is ensured. In addition, based on the ceramic blank prepared from the ceramic composite material, the invention also provides a ceramic blank degreasing method, which is used for being matched with the ceramic composite material to solve the problems that the ceramic blank is easy to deform and crack in the degreasing process and the like.
The invention discloses a photocuring resin-based ceramic composite material for additive molding, which can comprise ceramic powder and resin slurry; the ceramic powder accounts for 30-80% of the ceramic composite material by volume; the resin sizing agent comprises 5-30 parts by weight of light-cured monomer, 10-30 parts by weight of cross-linking agent monomer, 0.05-5 parts by weight of light-cured initiator and 0.01-1 part by weight of structural reinforcing agent. Wherein the refractive index of the photo-curable monomer is greater than or equal to 1.5, and/or the refractive index of the crosslinker monomer is greater than or equal to 1.5.
Preferably, the ceramic powder may be one or more of alumina, zirconia, aluminum nitride, silicon carbide, yttria, magnesia, silica, calcium oxide, bismuth oxide, hydroxyapatite, and tricalcium phosphate.
Preferably, the refractive index of the photocurable monomer is less than or equal to 1.8 and/or the refractive index of the crosslinker monomer is less than or equal to 1.8, thereby providing a ceramic composite system with a more uniform refractive index profile.
Preferably, the photo-curing monomer may be selected from one or more of 2-thiophenyl ethyl acrylate, bicyclo phenoxyethyl acrylate, o-phenylphenoxyethyl acrylate, and N-vinylcarbazole.
Preferably, the crosslinking agent monomer may have a benzene ring or a rigid group of an alicyclic structure.
Preferably, the cross-linking agent monomer may be selected from one or more of multifunctional aromatic urethane acrylate, ethoxylated bisphenol a acrylate.
Preferably, the photo-curing initiator may be selected from one or more of acyl oxide bony, diacyl oxide bony, benzil ketone, benzoin ether, thioxanthone, benzil ketal, acetophenone and benzophenone.
Preferably, the structural reinforcing agent of the present invention may be one or more of a helical single-walled nanotube and a helical multi-walled carbon nanotube. Wherein, the tube diameter of the carbon nano tube is preferably 10-20 nanometers, and the spiral diameter is preferably 50-200 nanometers.
Further, the resin syrup of the present invention may preferably further include 0.05 to 0.3 parts by weight of a structural reinforcing aid for improving the dispersion effect of the structural reinforcing agent. Preferably, the structure-enhancing additive may be one or more of benzoic acid polyethylene glycol quaternary ammonium nitrate and naphthoic acid polyethylene glycol quaternary ammonium nitrate, and has a molecular weight of 500-.
The ceramic composite material of the present invention may preferably further comprise 0.1 to 10 parts by weight of a powder stabilizer. Further, the powder stabilizer may include at least one dispersant and at least one permeability enhancer.
Preferably, the dispersant may be one or two selected from a polymeric hyperdispersant and a poly (ethyl) oxy quaternary ammonium salt. The polymeric hyperdispersant is preferably one or more selected from the group consisting of polyester hyperdispersant, polyether hyperdispersant, polyacrylate hyperdispersant and polyurethane block copolymer hyperdispersant, and has a molecular weight of 1000-3000.
Preferably, the permeability enhancer may be a substance containing a hydroxyl group, an amino group, a carboxyl group, or an ethoxy group. Further, the permeability enhancer may have a viscosity of less than 10mpa.s and a molecular weight of 200-.
Preferably, the permeability enhancer may be selected from one or more of amino acid type amphoteric surfactants, amino/oxysilane surfactants, and polyoxyethylene fatty alcohol ethers.
The resin syrup of the present invention may preferably further include 10 to 30 parts by weight of a polymerization inhibitor for resisting polymerization inhibition effect by metal ions from the ceramic powder.
Preferably, the polymeric immunity agent may be a multifunctional mercaptopropionate composition. The composition may include a multifunctional mercaptopropionate in combination with a vinyl ether diluent.
Preferably, the multifunctional mercaptopropionate is selected from one or more of trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis-3-mercaptopropionate, isophorone diurethane hexametaphosphate.
Preferably, the ratio of the multifunctional mercaptopropionate to the vinyl ether diluent may be 8:2 to 2: 8.
The resin paste of the present invention may preferably further include an interface enhancer in an amount of 5-20 parts by weight for rapid diffusion through the gaps between the ceramic powders. Preferably, the interface enhancer may be selected from one or more of 4-hydroxybutyl (meth) acrylate, hydroxyethyl (meth) acrylate, N-acryloyl morpholine.
The resin slurry of the present invention may preferably further comprise 5-20 parts by weight of a low-temperature pore-forming agent, and the temperature thereof is preferably 100-200 ℃. Preferably, the low-temperature pore-forming agent may be selected from the group consisting of Mn: 200-2000 linear poly aliphatic hydrocarbon, polyethylene glycol, aliphatic hydrocarbon and (meth) acrylate copolymer.
The resin syrup of the present invention may preferably further include 0.01 to 0.5 parts by weight of a polymerization inhibitor for inhibiting photopolymerization reaction caused by low-intensity light.
Preferably, the polymerization inhibitor may be selected from one or more of the phenol or benzoquinone series.
Another aspect of the present invention provides a degreasing method of a ceramic green body prepared using the ceramic composite material of the present invention, which may include a first degreasing process, a second degreasing process, a third degreasing process, and a fourth degreasing process, wherein the first degreasing process, the second degreasing process, the third degreasing process, and the fourth degreasing process are performed at first temperature, second temperature, third temperature, and fourth temperature, respectively, which are different from each other, and the first temperature, the second temperature, the third temperature, and the fourth temperature satisfy a gradually increasing relationship.
Preferably, the first temperature may be 100 ℃ to 200 ℃, the second temperature may be 250 ℃ to 350 ℃, the third temperature may be 400 ℃ to 600 ℃, and the fourth temperature may be 600 ℃ to 800 ℃.
Detailed Description
Hereinafter, exemplary embodiments of the present invention will be provided by way of examples in order to fully convey the spirit of the present invention to those skilled in the art to which the present invention pertains. Accordingly, the present invention is not limited to the embodiments disclosed herein.
The resin-based ceramic composite material for three-dimensional printing mainly comprises ceramic powder and resin slurry. Wherein, the ceramic powder is preferably selected from one or more of alumina, zirconia, aluminum nitride, silicon carbide, yttrium oxide, magnesium oxide, silicon oxide, calcium oxide, bismuth oxide, hydroxyapatite, tricalcium phosphate and the like. In the present invention, in order to reduce shrinkage during molding and to suppress the occurrence of surface cracking, the ceramic composite material is designed to have a high solid content. Preferably, the ceramic powder may account for 30-80% by volume of the ceramic composite system. Among them, the powder particle size may be preferably 0.1 to 25 μm.
However, such a design with high solid content may cause a series of disadvantages, such as poor dimensional accuracy of the formed ceramic green body, poor bonding force between the ceramic green body layers and the printing forming platform, cracking of part of the suspended structure or fine structure during the printing process, and even difficult forming. For this reason, the resin slurry is specially designed so as to provide excellent ceramic additive forming effect under a high solid content system.
In the present invention, the resin syrup may include a photo-curable monomer, but the photo-curable monomer has a lower viscosity and a higher refractive index; preferably, the viscosity is 1 to 150mPa.s and the refractive index is 1.5 to 1.8. Preferably, the photo-curing monomer may be selected from one or more of 2-thiophenyl ethyl acrylate (PTEA), bicyclo phenoxyethyl acrylate, o-phenylphenoxyethyl acrylate, and N-vinylcarbazole (NVC).
A cross-linking agent monomer may also be included in the resin syrup. In the present invention, the crosslinker monomer is selected to be a composition having a higher refractive index; preferably, the higher refractive index is 1.5-1.8. In addition, the cross-linking agent monomer also has a rigid structure, and preferably has a rigid group with a benzene ring or an alicyclic structure, so that the hardness and rigidity of the ceramic slurry system after curing can be improved, and the details of the ceramic blank body can be well embodied. Preferably, the cross-linking agent monomer may be selected from one or more of multifunctional aromatic urethane acrylate, ethoxylated bisphenol a acrylate.
Preferably, in the resin syrup of the present invention, the photo-curing monomer may be used in an amount of 5 to 30 parts by weight and the crosslinking agent monomer in an amount of 10 to 30 parts by weight.
Due to the optimized design of the resin slurry on the refractive indexes of the light curing monomer and the cross-linking agent monomer, the refractive index distribution in the ceramic composite material system is more uniform, and compared with the prior art (which usually adopts monomers and cross-linking agent materials such as HDDA, TMPTA and the like with the refractive indexes of 1.44-1.46), the scattering phenomenon caused by the refractive index difference can be obviously reduced, so that the curing depth of the ceramic composite material is effectively increased, the bonding force between ceramic green body layers is enhanced, and the performance of the ceramic composite material system with high solid content is particularly improved.
The resin syrup of the present invention may further include a photo-curing initiator for adjusting curing effect. Preferably, the photo-curing initiator may be selected from one or more of acyl oxide bony, diacyl oxide bony, benzoin ketone (benzoin), benzoin ether, thioxanthone, benzil ketal, acetophenone and benzophenone.
Preferably, in the resin syrup of the present invention, the photoinitiator may be used in an amount of 0.05 to 5 parts by weight.
In order to improve the tensile strength of the shaped part, a structural reinforcement may also be included in the ceramic composite material of the present invention. Preferably, the structural reinforcing agent may be selected from helical single-walled nanotubes or helical multi-walled carbon nanotubes. In the present invention, the helical carbon nanotubes are particularly preferred as the structural reinforcing agent because they can better connect the surrounding slurry and give better mechanical effects, particularly tensile properties, than the linear carbon nanotubes; the nanotube is used as a structure reinforcing agent, and compared with other fiber reinforcing materials, the nanotube can be removed through oxidation reaction in a degreasing stage, and no residue is left to influence the final ceramic performance, so that the nanotube can be matched with the ceramic blank degreasing method to obtain the optimal forming effect.
Preferably, the helical carbon nanotube has a tube diameter of 10 to 20 nm and a helix diameter of 50 to 200 nm.
The applicant has further found that the dispersion effect of the carbon nanotubes in the resin system of the present invention is not very ideal, and therefore, in order to enhance the effect of the structural reinforcing agent, carbon nanotubes, in the ceramic system of the present invention, it is also proposed to add an auxiliary agent capable of improving the dispersion effect of the structural reinforcing agent in the ceramic system, i.e., a structural reinforcing auxiliary agent, to the ceramic material. It was found through analytical studies that benzoic acid polyethylene glycol quaternary ammonium nitrate or naphthoic acid polyethylene glycol quaternary ammonium nitrate can provide the best improvement effect on the dispersion of carbon nanotubes in the ceramic system of the present invention. Preferably, the structural reinforcing aid has a molecular weight of 500-.
Preferably, the structural reinforcing agent is used in an amount of 0.01 to 0.1 parts by weight, and the structural reinforcing aid is used in an amount of 0.05 to 0.3 parts by weight. In order to improve the stability of the ceramic composite system and provide proper viscosity in a high solid content environment, a powder stabilizer may also be included in the resin syrup of the present invention.
According to the present invention, the powder stabilizer may include at least one dispersant component and at least one permeability enhancer component. In the present invention, since the ceramic composite material system of the present invention exhibits a strong polarity, it is preferable to use a polymeric hyperdispersant and/or a poly (ethyl) oxy quaternary ammonium salt as a dispersant so as to form a good matching relationship with the overall polar system, wherein the poly (ethyl) oxy quaternary ammonium salt as a cationic dispersant can provide the ceramic system with an electrostatic stabilization effect, and the polymeric hyperdispersant can provide the ceramic system with a steric stabilization effect. Preferably, the hyperdispersant may include polyester type hyperdispersants, polyether type hyperdispersants, polyacrylate type hyperdispersants, and polyurethane block copolymer hyperdispersants, which will be able to form a good match with the main component of the ceramic material system of the present invention. Research shows that when the molecular weight of the hyperdispersant is between 1000-3000, the hyperdispersant can provide better compatibility with the ceramic material system of the invention and moderate system viscosity. However, the inventors of the present invention have found through studies that the theoretical effect cannot be well achieved when the dispersant component is added to the ceramic composite system alone, and therefore, the penetration enhancer component is introduced into the powder stabilizer of the present invention to cooperate with the dispersant component, so as to provide a good powder stabilization effect for the whole ceramic composite system. For example, the permeability enhancer component may work in conjunction with the dispersant to enhance the wetting of the dispersant molecules in the ceramic powder, which is particularly advantageous for improving the effect of the dispersant in high solids environments. In the present invention, the permeability enhancer is preferably a small-molecular low-viscosity substance containing a anchor group such as a hydroxyl group, an amino group, a carboxyl group or an ethoxy group, wherein the viscosity is preferably less than 10mPa.S, and the molecular weight is preferably 200-. By means of the small-molecule reinforcing agent, a stable bridge can be established between the large-molecule dispersing agent and the ceramic powder, so that the whole ceramic system is endowed with stable and proper viscosity. Experiments prove that the permeability enhancer can allow the addition amount of the ceramic powder to be increased from 40% to 80% by volume in the ceramic material system, and simultaneously, the viscosity is reduced from 3Pa.S to less than 1Pa.S, so that the ceramic material is more suitable for the requirement of three-dimensional printing.
More preferably, the permeability enhancer may employ amino acid type amphoteric surfactants (the number of C atoms in the molecular chain is preferably between 8 and 12), amino/oxysilane surfactants, and polyoxyethylene fatty alcohol ethers (the number of EO (ethylene oxide) therein is preferably between 5 and 10).
Preferably, in the resin syrup of the present invention, the powder stabilizer may be used in an amount of 0.1 to 10 parts by weight.
The resin paste of the present invention may preferably further include a polymerization inhibitor for resisting polymerization inhibition effects caused by various metal ions from the ceramic powder, thereby allowing the system to achieve a sufficient degree of polymerization and ensuring sufficient strength of the formed mold.
In the present invention, a polyfunctional mercaptopropionate composition is preferably used as the polymeric immunity agent. The multifunctional mercaptopropionate compositions of the present invention may be a combination of multifunctional mercaptopropionate and a vinyl ether diluent, and the ratio of the two may preferably be between 8:2 and 2: 8. Preferably, the multifunctional mercaptopropionate may be selected from one or more of trimethylolpropane tris (3-mercaptopropionate) (TMPMP), pentaerythritol tetrakis-3-mercaptopropionate (PETMP), isophorone dicarbamate hexametaphosphate. The vinyl ether diluent may be triethylene glycol divinyl ether (DVE-3).
By adding the polyfunctional mercapto propionate composition as a polymerization interference inhibitor into the system, good flexibility can be provided for the ceramic composite material after curing, stress is relieved, oxygen inhibition during curing and interference of metal ions in the ceramic powder body on curing are overcome, and double bond conversion rate is improved; meanwhile, the polymerization interference inhibitor has higher refractive index, which is beneficial to improving the refractive index of the resin slurry and improving the curing depth of the ceramic composite material system.
Preferably, in the resin syrup of the present invention, the polymeric anti-interference agent may be used in an amount of 10 to 30 parts by weight.
According to the invention, an interface reinforcing agent component is preferably further arranged in the ceramic slurry, and can be rapidly diffused to penetrate through powder gaps and reach an interface, so that the mechanical strength between the model layers is ensured. By means of the components, the bonding of resin to ceramic powder can be increased, the bonding force between ceramic blank layers can be increased, and the bonding between the ceramic blank and the printing platform can be promoted to be firmer. Preferably, the interface enhancer may be selected from one or more of 4-hydroxybutyl (meth) acrylate, hydroxyethyl (meth) methacrylate, and N-Acryloylmorpholine (ACMO).
Preferably, in the resin syrup of the present invention, the interfacial enhancer may be used in an amount of 5 to 20 parts by weight.
In order to provide an improved degreasing effect of the green body, a low-temperature pore-forming agent may be further added to the ceramic composite material of the present invention, and the low-temperature pore-forming agent is used to generate voids between ceramic particles at a relatively low temperature, and provide a rapid diffusion path for oxygen and organic substances, thereby accelerating a degreasing process. Thus, the low temperature pore former may be selected to be a material having a relatively low melting point and which should exhibit good compatibility with the resin slurry system of the present invention. Preferably, the low temperature pore former may have a melting point of 100-200 ℃. Preferably, the low temperature pore former may be selected from the group consisting of Mn: 200-2000 linear poly aliphatic hydrocarbon, polyethylene glycol, aliphatic hydrocarbon and (meth) acrylate copolymer. The existence of the low-temperature pore-forming agent enables a favorable oxygen-enriched environment and a favorable flow channel to be formed in the blank body at the initial stage of the blank body degreasing process, thereby providing convenient conditions for the subsequent degreasing process and realizing gradual step-by-step degreasing.
Preferably, in the resin syrup of the present invention, the low-temperature pore-forming agent may be used in an amount of 5 to 20 parts by weight.
In the photocuring molding process, scattered light of low intensity is formed due to the presence of phenomena such as scattering, thereby causing an undesirable photopolymerization reaction. In order to suppress such photopolymerization at low light intensity, the resin syrup of the present invention is further provided with a polymerization inhibitor component. Preferably, the polymerization inhibitor may be selected from one or more of the phenol or benzoquinone series.
Preferably, in the resin syrup of the present invention, the polymerization inhibitor may be used in an amount of 0.01 to 0.5 parts by weight.
It should be particularly noted that, as proved by practice, the ceramic composite system containing the above-mentioned components in the preferred amounts can best meet the requirement of forming high-quality ceramic parts under the environment of high solid content with the ceramic powder accounting for 30-80% by volume of the ceramic composite system, and the matching relationship among the components in the system is the most appropriate, so as to provide the best synergistic action relationship.
In preparing the ceramic composite material of the present invention, as an exemplary manner, the following steps may be employed: firstly, adding the components such as the low-viscosity light-cured monomer, the cross-linking agent monomer, the powder stabilizer, the polymerization anti-interference agent and the interface reinforcing agent into a clean glass ware, and fully and uniformly stirring to form a premixed solution; then, adding a proper amount of ceramic powder into the premixed liquid, stirring and dispersing uniformly at the speed of 300-600r/min, and then placing into a ball milling tank for ball milling for at least 8 h; finally, adding a proper amount of initiator and polymerization inhibitor, and uniformly mixing for later use.
According to the invention, through the component selection and dosage design of the ceramic composite material, especially under the condition that resin monomers and cross-linking agent components with proper polarity and refractive index, structure reinforcing agent, powder stabilizer, polymerization interference inhibitor and interface reinforcing agent are introduced, the refractive index difference between a resin system and ceramic powder can be reduced while the reaction activity of the whole system is kept, the transmission depth of a ceramic slurry system is improved, and the size error caused by light scattering in the additive forming process is effectively reduced; meanwhile, the active monomer and the ceramic powder material can be ensured to have good affinity, and strong intermolecular forces such as hydrogen bonds can be formed after the active monomer and the crosslinking component are cured, so that the bonding force between the ceramic blank layers is increased, the bonding force between the ceramic blank and the metal printing platform is correspondingly increased, the separation phenomenon of the ceramic blank and the platform is effectively reduced, and the problem of surface cracks of the ceramic blank is well solved. The addition of the structural reinforcing agent obviously improves the tensile strength of the formed part, and a suspended structure or a fine structure can be well presented in the printing process.
In addition, when the ceramic green body is prepared by using the ceramic composite material, a ceramic green body resin system in the prior art is concentrated in a certain narrow temperature range in a degreasing process due to the fact that resin structures are similar, chemical decomposition is carried out, rapid degreasing is carried out, a green body supporting structure is broken in a short time, and the ceramic structure is deformed and even cracked. By means of the ceramic composite material, due to the unique component design scheme, the ceramic blank formed by the ceramic composite material can be gradually degreased in a wider temperature range, so that the problem that the ceramic blank is deformed and cracked in the degreasing process in the prior art is effectively solved, and the high-quality ceramic additive forming effect is provided.
Specifically, the ceramic green body formed based on the ceramic composite material of the present invention may be degreased by the following method. The degreasing method according to the present invention includes a first degreasing process, a second degreasing process, a third degreasing process, and a fourth degreasing process, wherein the first degreasing process, the second degreasing process, the third degreasing process, and the fourth degreasing process are performed at first temperature, second temperature, third temperature, and fourth temperature, respectively, which are different from each other, and the first temperature, the second temperature, the third temperature, and the fourth temperature satisfy a gradually increasing relationship.
As a preferred example, the first temperature may be between 100 ℃ and 200 ℃ in the first degreasing process. At this time, the low temperature pore-forming agent, such as inert low molecular weight polyolefin, polyethylene glycol, polyolefin- (meth) acrylate copolymer, etc., will be removed from the green material network structure in a fluid form, so that the green body has more voids while keeping the basic structure intact, providing convenience for oxygen to enter the ceramic green body structure.
In a subsequent second degreasing process, the second temperature may be increased to between 250 ℃ and 350 ℃. In this temperature range, the polyurethane groups and polyether groups in the ceramic green body start to oxidize or thermally decompose.
During the following third degreasing process, the third temperature may be continuously raised to between 400 ℃ and 600 ℃. In the process, residual aromatic groups and other groups in the embryo body are subjected to thermal oxidative decomposition and degreasing.
Finally, in a fourth degreasing process, a fourth temperature may be set between 600 ℃ and 800 ℃ in order to finish soaking oxidation of all the residual char.
Therefore, by means of the ceramic composite material, the ceramic blank supporting structure is prevented from being intensively disintegrated in a short time in the degreasing process, and the deformation and cracking phenomena of the ceramic structure are effectively relieved.
Although the photocurable resin-based ceramic composite material and the method for degreasing a green body thereof according to the present invention have been described in detail with reference to specific embodiments, those skilled in the art will readily appreciate that the above embodiments are only exemplary for illustrating the principles of the present invention and do not limit the scope of the present invention, and that various combinations, modifications and equivalents of the above embodiments may be made by those skilled in the art without departing from the spirit and scope of the present invention.
Claims (22)
1. A photocuring resin-based ceramic composite material for additive molding comprises ceramic powder and resin slurry; the ceramic powder accounts for 30-80% of the ceramic composite material by volume; the resin sizing agent comprises 5-30 parts by weight of light-cured monomer, 10-30 parts by weight of cross-linking agent monomer, 0.05-5 parts by weight of light-cured initiator and 0.01-0.1 part by weight of structural reinforcing agent, wherein the refractive index of the light-cured monomer is greater than or equal to 1.5, and/or the refractive index of the cross-linking agent monomer is greater than or equal to 1.5;
the resin slurry also comprises 10-30 parts by weight of a polymerization interference inhibitor for resisting polymerization inhibition effect generated by metal ions from the ceramic powder;
the ceramic powder is one or more of alumina, zirconia, aluminum nitride, silicon carbide, yttrium oxide, magnesium oxide, silicon oxide, calcium oxide, bismuth oxide, hydroxyapatite and tricalcium phosphate;
the refractive index of the photo-curable monomer is less than or equal to 1.8, and/or the refractive index of the crosslinker monomer is less than or equal to 1.8.
2. The ceramic composite of claim 1, wherein the photo-curable monomer is selected from one or more of 2-thiophenylethyl acrylate, dicyclo-phenoxyethyl acrylate, o-phenylphenoxyethyl acrylate, and N-vinylcarbazole.
3. The ceramic composite material according to claim 1, wherein the cross-linker monomer has a benzene ring or a rigid group of an alicyclic structure.
4. The ceramic composite material according to claim 3, wherein the crosslinker monomer is selected from one or more of multifunctional aromatic urethane acrylates, ethoxylated bisphenol A acrylates.
5. The ceramic composite of claim 1, wherein the photo-curing initiator is selected from one or more of acyl oxide bony, diacyl oxide bony, benzil ketone, benzoin ether, thioxanthone, benzil ketal, acetophenone, and benzophenone.
6. The ceramic composite of claim 1, wherein the structural reinforcing agent is one or more of helical single-walled nanotubes and helical multi-walled carbon nanotubes.
7. The ceramic composite of claim 6, wherein the carbon nanotubes have a tube diameter of 10 to 20 nanometers and a spiral diameter of 50 to 200 nanometers.
8. The ceramic composite of claim 1, wherein the resin paste further comprises 0.1 to 10 parts by weight of a powder stabilizer comprising at least one dispersant and at least one permeability enhancer.
9. The ceramic composite of claim 8, wherein the dispersant is a polymeric hyperdispersant.
10. The ceramic composite of claim 9 wherein the polymeric hyperdispersant is selected from one or more of polyester hyperdispersant, polyether hyperdispersant, polyacrylate hyperdispersant, and molecular weight is 1000-.
11. The ceramic composite of claim 8, wherein the permeability enhancer is a hydroxyl, amino, carboxyl, or ethoxy containing material.
12. The ceramic composite of claim 11 wherein the permeability enhancer has a viscosity of less than 10mpa.s and a molecular weight of 200-400.
13. The ceramic composite of claim 12, wherein the permeability enhancer is selected from one or more of an amino acid type amphoteric surfactant, an amino/oxysilane surfactant, and a polyoxyethylene fatty alcohol ether.
14. The ceramic composite of claim 1, wherein the polymeric immunity agent is a multi-functional mercaptopropionate composition comprising a combination of multi-functional mercaptopropionates and vinyl ether diluents.
15. The ceramic composite of claim 14, wherein the multifunctional mercaptopropionate is selected from one or more of trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis-3-mercaptopropionate, isophorone diurethane hexametaphosphate, and the ratio of multifunctional mercaptopropionate to vinyl ether diluent is 8:2 to 2: 8.
16. The ceramic composite of claim 1, wherein the resin paste further comprises 5-20 parts by weight of an interface enhancer for rapid diffusion through gaps between the ceramic powders.
17. The ceramic composite of claim 16, wherein the interfacial enhancer is selected from one or more of 4-hydroxybutyl (meth) acrylate, hydroxyethyl (meth) acrylate, N-acryloylmorpholine.
18. The ceramic composite material according to claim 1, wherein the resin paste further comprises 5 to 20 parts by weight of a low-temperature pore-forming agent.
19. The ceramic composite of claim 18 wherein the low temperature pore former is selected from the group consisting of Mn: 200-2000 linear poly aliphatic hydrocarbon, polyethylene glycol, aliphatic hydrocarbon and (meth) acrylate copolymer.
20. The ceramic composite material according to claim 1, wherein the resin paste further comprises 0.01 to 0.5 parts by weight of a polymerization inhibitor for inhibiting photopolymerization reaction caused by low-intensity light; the polymerization inhibitor is selected from one or more of phenol or benzoquinone series.
21. A degreasing method of a ceramic green body manufactured using the ceramic composite material according to any one of claims 1 to 20, comprising a first degreasing process, a second degreasing process, a third degreasing process, and a fourth degreasing process, wherein the first degreasing process, the second degreasing process, the third degreasing process, and the fourth degreasing process are performed at a first temperature, a second temperature, a third temperature, and a fourth temperature, respectively, which are different from each other, and the first temperature, the second temperature, the third temperature, and the fourth temperature satisfy a gradually increasing relationship.
22. The degreasing method of claim 21, wherein the first temperature is 100 ℃ to 200 ℃, the second temperature is 250 ℃ to 350 ℃, the third temperature is 400 ℃ to 600 ℃, and the fourth temperature is 600 ℃ to 800 ℃.
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| CN109227877A (en) * | 2018-10-31 | 2019-01-18 | 南京航空航天大学 | A method of based on the molding porous bone hydroxylapatite ceramic cytoskeleton of photocuring 3D printing technique |
| CN110092652A (en) * | 2019-04-23 | 2019-08-06 | 四川大学 | Bioactivity, porous ceramic preparation based on the face DLP exposure forming technique |
| CN110395991A (en) * | 2019-07-25 | 2019-11-01 | 西安增材制造国家研究院有限公司 | A kind of photocuring silicon nitride ceramics creme and preparation method thereof |
| CN112171848A (en) * | 2020-09-29 | 2021-01-05 | 江西金石三维智能制造科技有限公司 | Photocuring silicon carbide ceramic slurry and preparation method and application thereof |
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